Catalytic process for hydrolyzing organic halides



Oct. 25, 1932. R. JENKINS ET AL 1,834,710

CATALYTIC PROCESS FOR HYDROLYZING ORGANIC HALIDES Filed Nov. 17, 1928 TO (ON BENSER POROILS s/Lloq BED METFLL/C PREHEHTER'H 10 V/YPORS POROUS SlL/C/LBLID COPPER SHHVI/VGS B'yv W WAtmmey duction cl phenol by c Patented out. 25, 1932 UNITED. STATE PATENT orricr.

I BUBBELL L. JENKINS, OI ANNIS'I'ON, ALABAIA, AND TAKES I. NORRIS, OF CAMBRIDGE,

IASSACHUSETTB, ASSIGNOBS TO SWAIN SEARCH, INC A CORPORATION 01' ALABAMA.

CATALYTIC PROCESS FOB HYDBOLYZING ORGANIC EALIDEB Application filed number 1?, 1m. lerhl Io. 320,000.

@ur invention relates to a catalyticprocess, and more particularly to means whereby the activit of the catalytic agent may be maintaine Specifically, it relates to im- 55 proved means whereby a catalytic agent, for

example, silica gel or silica skeleton, hereina'iter referred to as a highly porous body, may be used for the hydrolysis reaction of an organic halide. with steam to form organic 21o hydrony compounds, such as phenols or alcoholso An obyect o l this invention is the provision oil a process for hydrolyzmg organic halides on a catalytic body by means of steam, is wherein the ethciency said catalytic body is built maintained at a degree "while in continuous use. r i

A further object or our to provide an improved process or ing a porous silic yet, the e cicncy oi the catalyst i enl? need impregnation with a metallic compound, and wherein said metallic compound is c ntinu ally supplied in '"volatiliaed form reaction mixture.

' The catalyst is characterized by compris ing a highly porous body as its-major ingredient, and. a metallic salt or combination of metallic salts as its minor ingredient. The metallic saltmay be obtained from a metal alloys of a metal, or compounds thereof, which form volatile salts undercondi-" tions which exist in the use of our catalyst.

35 Our catalyst and the method of association of" the metallic salt, is adapted to use in a variety ogf reactions; and for purposes of illustration in this apglication, we will refer to its use in the hy rolysisof monochlorbenphenol.

, It has already been vproposed to hydrolyze the halidesof hydrocarbons by passing a rezene andwat er 1n the vapor phase,to form chlorbenzene and steam pass over This rocess has been found to be especially useful in the production of phenol from monochlorbenzene, the monochlorbenzene, to-

gether with steam, and heated to around 550 0., being passed through the porous silica catalyst bed. In carrylng out this process,

we have found that the activity of the cata-, lyst bed is greatly increased by having ass0- elated therewith a metallic catalyzing agent. The increase in activity brought about by the association ofthe metallic ca'talyzingagent with the porous silica catalyst is, in some instances, ten times that of the porous silica catalyst alone.

With reference to the use of the catalyst in the above mentioned reaction, in our research We have found when impregnating a highly-porous body with a metallic salt by of an aqueous solution and subsequently evaporating the water, the catalyst so obmoval of the highly porous body from the reaction chamber is unnecessary, and the catalyst is always at its maximum elfiiciency. While other metals, as iron, bismuth, tin and cobalt, will form volatile saltsand, when associated with a highly porous body, increase the catalytic activitythereof, we will'refer to to the use of co per, alloys of. copper or-compounds thereo these being the preferred sources of. metallic salt. a We have found that if a per shavings be interposed ina vapor stream before it passes through a porous body, such as, before mentioned the vapors of monobody of cop- 86 action mixture'in a vapor phase over a heat- 'ed catalyst bed comprised of porous silica. shavings, there is sufiicient action on the shavings'to form a very small quantity of cuprous chloride, which is vaporized and passes along with the reaction mixture over the porous body. The association of the metallic salt vapors and the highly porous body result in a catalytic action on the reaction mixture whereby phenol and hydrochloric acid are formed,saidcatalytic action being far greater than is obtained with the use of the porous body alone. Instead of placing copper shavings' in the gas stream, the vapors may be preheated ina preheater made of copper or alloys thereof, such as yellow brass, and in either case suflicient copper will be supplied to the gas stream to maintain optimum cata l tic activity. It is also satisfactory to pass the reaction mixture over copper oxide.

In order that our invention may be clearly 'understood, reference will now be had to the accompanying diagrammatic drawing wherein Figs, 1 and 2 show respectively alternate methods of carrying out the invention.

Referring first to Fig. 1, the reaction mixture in the form of vapor passes through a metallic prehe'ater 10 which is preferably made of copper or alloys thereof, and wherein the vapors are heated to around 550 U The heating of the vapors in this preheater supplies sufiicient metallic salt in a vapor form to the reaction mixture to maintain optimum catalytic activity. After passing the preheater 10'the vapors flow through a porous silica catalyst bed which is also heated by means of suitable electric heating elements 12 and 13 to around 550 C. After passing through the porous silica bed, the vapors may be condensed and the phenol formed separated in a manner well known in the art. l

Referring now to Fig. 2, we may provide a casing 16 inclosing a porous silica catalyst bed 17 and a bed of copper shavings 1-8. The silica bed and the bed of copper shavings are both heated to around 550 C. by means of suitable electric heating elements 19 and 21. With this apparatus, the vapors pass through the heated bed of copper shavings and thence immediately through the porous silica bed,'carrying with them a sufiicient amount of. volatilized metallic salt to greatly increase the catalytic activity of the porous silica bed.

From the foregoing it will be apparent that its catalytic activity and maintaining its high order of catalytic activity.

While we have described two ways of carrylng out our invention, it will be obvious to thoseskilled in the art that it is not so limited but is susceptible of various changes and modifications without departing from the spirit thereof, and we desire therefore that only such limitaions shall be placed aaeano thereupon as are imposed by the prior art, or as are specifically set forth in the appended claims.

What we claim is:

1. An improved method of producing ,a catalytic reaction which consists in passing a reaction mixture in the vapor phase over a metal having catalytic properties and being capable of forming a volatile salt under the conditions of use, and then passing said volatile metal salt commingled with the reaction mixture through a bed comprising a highly porous body.

2. An improved method of producing a catalytic reaction which consists in passing a reaction mixture in the vapor phase over a metallic salt having catalytic properties and being capable of forming a volatile salt under the conditions of use, and then passing said volatile metal salt together with the reaction mixture through a bed consisting of a highly porous body. 7

3. The method of maintaining the rate of a catalytic reaction wherein a porous body is employed as a catalyst which comprises subjecting said body to a vapor stream of the reaction mixture associated with a volatilized metallic compound having catalytic properties.

4. The method of producing a catalytic re action which consists in passing in the vapor phase the products to be combined together with a volatilized metallic salt having catalytic properties through a porous silica catalyst bed.

5. The method of producng phenol which consists in passing monochlorbenzene in the vapor phase together with steam and a volatilized metallic salt, through a porous silica catalyst'bed.

6. An improved method of effecting the hydrolysis of an organic halide which consists in passing a reaction mixture of said halide and water both in the vapor phase over a metallic compound having catalytic properties when combined with a highly porous body to form a metallic salt in association with said mixture, then passing said reaction mixture together with the metallic salt through a bed comprising said highly porous body.

7. An improved method of producing phenol which consists in passing vapor containing monochlorbenzol, steam and a volatilized coper salt over a porous silica skeleton, followed by condensing and separating the phenol from the reaction mixture.

8. An improved method a of producing phenol which consists in passing vapor contaming monochlorbenzol and steam over copper oxide and at a temperature high enough to produce a volatilized copper salt, and then passlng said vapor over aporous silica skele- 9. In a process of producing phenol by catalytic hydrolysis of monoclorbenzene, the

steps which comprise passing in the vapor phase the reaction mixture at a tem erature above 500 C. over coper oxide, and t en over a highly porous silica catalyst bed.

10. The method of producing a catalytic reaction which consists in passing a reaction mixture in the vapor phase over a substance havingcatalytic properties and being capable of forming a volatile metal salt under the conditions of use, and then passing said volatile metal salt commingled with the reaction mixture through a bed comprising a highly porous body.

In testimony whereof we aflix our signatures.

RUSSELL L. JENKINS. JAMES F. NORRIS. 

